OE?A?INUeEEE AeA?AEAAIEE O?I?EI-OAOIIEIA?*IEE
OI?AA?NEOAO
A?IINUeEA ETHAeIEEA A?EOI??AIA
OAeE 543.253:546.96+547.47
AIEUeOAIIA?IIAO??ss Ru(IV) A I?ENOOIINO? IENEEENEIO
OA ?? CANOINOAAIIss A AIAE?C?
Niaoe?aeuei?noue 02.00.02 – aiae?oe/ia o?i?y
AAOI?AOA?AO
aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy
eaiaeeaeaoa o?i?/ieo iaoe
Aei?i?iiao?ianuee – 1999
Aeena?oaoe??th ? ?oeiien.
?iaioa aeeiiaia ia eaoaae?? aiae?oe/ii? o?i?? Euea?anueeiai aea?aeaaiiai
oi?aa?neoaoo ?iai? ?aaia O?aiea, I?i?noa?noaa ina?oe Oe?a?ie.
Iaoeiaee ea??aiee: eaiaeeaeao o?i?/ieo iaoe, aeioeaio,
A?oaeaanueea Oaiaeic?y ss?ineaa?aia,
Euea?anueeee aea?aeaaiee oi?aa?neoao
?i. ?.O?aiea,
aeioeaio eaoaae?e aiae?oe/ii? o?i??
Io?oe?ei? iiiiaioe:
aeieoi? o?i?/ieo iaoe, i?ioani? Oeeaaiie Ethaeieea Iaae?aia,
Aei?i?iiao?ianueeee aea?aeaaiee oi?aa?neoao, i?ioani? eaoaae?e
aiae?oe/ii? o?i??
eaiaeeaeao o?i?/ieo iaoe, aeioeaio Oeny/iee Aeaaeeneaa Iao?iae/,
Aea?aeaaia iaoaeo?a?eia aeaaeai?y Oe?a?ie, aeioeaio eaoaae?e aiae?oe/ii?
? o?ce/ii? o?i??
I?ia?aeia onoaiiaa: Aea?aeaaiee oi?aa?neoao “Euea?anueea iie?oaoi?ea”
Caoeno a?aeaoaeaoueny “ 4 ” /a?aiy 1999 ?ieo i 13.30 aiae a aoae. 220
ia can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 08.078.01 i?e
Oe?a?inueeiio aea?aeaaiiio o?i?ei-oaoiieia?/iiio oi?aa?neoao? ca
aae?anith: 320005, Aei?i?iia?ianuee. i?. Aaaa??ia, 8.
C aeena?oaoe??th iiaeia iciaeiieoenue a iaoeia?e a?ae?ioaoe?
Oe?a?inueeiai aea?aeaaiiai o?i?ei-oaoiieia?/iiai oi?aa?neoaoo.
Aaoi?aoa?ao ?ic?neaii “ 29 ” ea?oiy 1999 ?ieo.
A/aiee nae?aoa? niaoe?ae?ciaaii?
a/aii? ?aaee, e.o.i., aeioeaio
I?i?aeea ?.Ae.
Caaaeueia oa?aeoa?enoeea ?iaioe
Aeooaeuei?noue oaie. ?ioaineaiee ?icaeoie aeaeo?ii?ee noeioethaaa iiooe
? neioac iiaeo iaoa??ae?a c iaiao?aeieie iioe/ieie, ei?ic?eieie,
aeaeo?iiaai?oieie aeanoeainoyie. Iaeiith ?c neeaaeiaeo oeeo iaoa??ae?a ?
?ooai?e oa eiai niieoee. Oe?iea canoinoaaiiy aeaiaioo aenoaa? aei?noe?
aeiiae aei iaoiae?a eiio?ieth, ye? iio?aaothoue ?ic?iaee iaae?eieo,
/ooeeaeo, naeaeoeaieo ? aeni?anieo iaoiaeee aecia/aiiy ?ooai?th.
Oai?aoe/iith iniiaith aeey ?ic?iaee iiaeo iaoiaeee iiey?ia?ao?/iiai
aiae?co ? aea/aiiy o?i?? eiiieaenieo niieoe ?ooai?th. A aiae?oe/i?e
o?i?? ?ooai?th iniaeeai aaaeeeaeie ? eiiieaeni? niieoee c aenieeie
eiinoaioaie no?eeino?. Ia?niaeoeaieie c oaeeo i??eoaaiue ? eiiieaeni?
niieoee ?ooai?th c ieneeeneioaie, ye e?aaiaeaie, ye? caeaoi? ooai?thaaoe
eiiieaene ?c niaoeeo?/ieie oa?aeoa?enoeeaie. Aaaaoiaeaioaoi?noue
ieneeeneio, ye e?aaiae?a, iiaea i?eaiaeeoe aei ooai?aiiy eiiieaen?a c
caieiooeie oeeeeaie, ui ni?ey? i?aeaeuaiith no?eeino? ? onoiaiith
noaae?eiino? eiiieaeniooai?aiiy. Oea i?eaiaeeoue aei iaea?aeaiiy
i?i?iaeueiiai /enea ni?a?nioth/eo o?i?/ieo oi?i ?ooai?th ? ia? aaaeeeaa
cia/aiiy aeey iie?auaiiy a?aeoai?thaaiino? ?acoeueoao?a.
Oiio, ia iao iiaeyae, aeine?aeaeaiiy eiiieaeniooai?aiiy ?ii?a Ru(IV) c
ieneeeneioaie, aea/aiiy oiia aeii?ioaaiiy ie?aieo o?i?/ieo oi?i
eiiieaenieo niieoe, aeine?aeaeaiiy ?o aeaeo?io?i?/ieo ? o?i?/ieo
aeanoeainoae ? aeooaeueiith i?iaeaiith no/anii? aiae?oe/ii? o?i??
?ooai?th. ?ica’ycaiiy ?? ni?eyoeia ?ic?iaeaiith ? ai?aaaeaeaiith iiaeo
aiae?oe/ieo iaoiaeee.
Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. ?iaioa aeeiiaia
ca?aeii iaeiiai c iaoeiaeo iai?yie?a eaoaae?e (aea?aeathaeaeaoia oaia
2.20.1.1. oa athaeaeaoia oaia OA 655 A).
Iaoa ?iaioe: aeine?aeaeaiiy oi?i ?nioaaiiy ?ooai?th a iaeiiieaenoth/iio
na?aaeiaeu? oa a i?enooiino? ieneeeneio ? aeeea?aiiiaeo eeneio, aea/aiiy
aieueoaiia?ieo oa?aeoa?enoee ??cieo o?i?/ieo oi?i ?ooai?th (IV), iiooe ?
?ic?iaea iiaeo iaoiaeee aieueoaiia?iiao?e/iiai aecia/aiiy ?ooai?th.
Iaoeiaa iiaecia ?iaioe. Aia?oa i?iaaaeaii oa?iiaeeiai?/iee aiae?c
no?eeino? ??cieo o?i?/ieo oi?i ?ooai?th, cai?iiiiiaaii iiaee i?aeo?ae
aei ?ioa?i?aoaoe?? ?acoeueoao?a aecia/aiiy ca?yaeo ? nooiaiy
iie?ia?ecaoe?? i?e ni?a?nioaaii? aeae?eueeio /anoeiie c ??ciith
nooi?iith iie?ia?ecaoe??.
Iaoiaeii ?iiiiai iai?io aia?oa aeine?aeaeaii oi?ie ?nioaaiiy
?ooai?th(IV) a iaeiiieaenoth/eo ?ic/eiao i?e iecueeeo ai?noao ?ooai?th.
Aia?oa, aeei?enoiaoth/e a?ae?ienieiiieaene Ru(IV), niaeoioioiiao?e/ii,
aieueoaiia?iiao?e/ii oa iaoiaeii ?iiiiai iai?io aea/aii
eiiieaeniooai?aiiy ?ooai?th c ienaeaoiith, oeeo?aoiith ? oa?o?aoiith
eeneioaie. Anoaiiaeaii ni?aa?aeiioaiiy [iaoae]:[e?aaiae] oa oi?io
?nioaaiiy e?aaiaeo a eiiieaenieo niieoeao.
Iaoiaeii aieueoaiia?iiao??? aeine?aeaeaii eaoae?oe/i? aoaeoe, ui
aeieeathoue a i?ioean? a?aeiiaeaiiy ?ooai?th oa aieea ieneeeneio
(oeeo?aoii? ? oa?o?aoii?), ienaeaoii? eeneioe oa aeayeeo iai?aai?/ieo
ai?ii?a ia aaee/eio eaoae?oe/iiai no?oio. Aeine?aeaeaiee eaoae?oe/iee
aoaeo aeei?enoaiee aeey ?ic?iaee iaoiaeeee aieueoaiia?iiao?e/iiai
aecia/aiiy ai?noo ?ooai?th a neeaaeieo ia’?eoao.
Iaoeiaa ? i?aeoe/ia oe?ii?noue. Io?eiai? aenia?eiaioaeuei? aeai?
?icoe?ththoue a?aeiiino? i?i o?i?/i? oa aeaeo?io?i?/i? aeanoeaino?
a?ae?ienieiiieaen?a ?ooai?th(IV) oa eiai eiiieaenieo niieoe.
?ic?iaeaia ? ai?iaiaaia iaoiaeeea aieueoaiia?iiao?e/iiai aecia/aiiy
?ooai?th a neeaaeieo ia’?eoao. Iieacaia iiaeeea?noue aeei?enoaiiy
ieneeeneio ye aeiaaaee aei iiey?ia?ao?/iiai oiio c iaoith i?aeaeuaiiy
/ooeeaino? aieueoaiia?iiao?e/iiai aecia/aiiy ?ooai?th.
Aenia?eiaioaeueia aea/aiiy eaoae?oe/ieo oa aaoieaoae?oe/ieo i?ioean?a a
nenoaiao c ?ooai??i ?icoe?th? aaco aeey ?ic?iaee iiaeo iaoiaeee
aecia/aiiy, a oaeiae ?icoe?th? eiei nenoai, yeei aeanoea? aeine?aeaeai?
aoaeoe.
?acoeueoaoe aeine?aeaeaiiy eiiieaeniooai?aiiy ?ii?a Ru(IV) c
ieneeeneioaie iiaeooue aooe aacith aeey oe?eani?yiiaaiiai iiooeo ?ioeo
niieoe ?ooai?th c i?aai?/ieie eeneioaie.
Iniaenoee aianie aeena?oaioa. Aiae?c e?oa?aoo?ieo aeaieo,
aenia?eiaioaeuei? ?iaioe ii aeine?aeaeaiith oi?i ?nioaaiiy ?ii?a
?ooai?th a iaeiiieaenoth/eo na?aaeiaeuao oa a i?enooiino? ieneeeneio,
aeine?aeaeaiiy eaoae?oe/ieo oa aaoieaoae?oe/ieo i?ioean?a a ?ic/eiao c
iaeei ai?noii ?ooai?th i?iaaaeai? aaoi?ii aeena?oaoe?? naiino?eii
ca?aeii c aeac?aeaie iaoeiaiai ea??aieea. Oa?iiaeeiai?/iee aiae?c
no?eeino? ??cieo o?i?/ieo oi?i ?ooai?th i?iaaaeaii ni?eueii c aeieoi?ii
oaa?e?oao o?i?/ieo iaoe Iiaa?ii ?.A. – iaoeiaei ni?a?ia?oieeii ?inoeoooo
o?i?? Aeaaeai?? Iaoe ?anioae?ee Iieaeiaa.
Ai?iaaoe?y ?iaioe. Iniiai? ?acoeueoaoe ?iaioe aeiiia?aeaee ia
i?aeia?iaei?e eiioa?aioe?? c o?ceee ? o?i?? iai?ai?ia?aeiee?a o
*a?i?aoeyo (1995?.), ca?oieo iaoeiaeo eiioa?aioe?yo ni?a?ia?oiee?a
Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?iai? ?aaia O?aiea (1995, 1996,
1997??.), anaoe?a?inueeeo eiioa?aioe?yo c aiae?oe/ii? o?i?? o Ee?a?
(1995?.) oa a Oaeai?iae? (1998?.), iaoeiai-i?aeoe/ieo eiioa?aioe?yo
“Euea?anuee? o?i?/i? /eoaiiy” (1995, 1997??.), eiioa?aioe??
i?ioani?nueei-aeeeaaeaoeueeiai neeaaeo ? ani??aio?a Euea?anueei?
eiia?oe?eii? aeaaeai?? (1996?.), Ia?oiio cao?aeii-oe?a?inueeiio
neiiic?oi? c aaeni?aoe?? ? o?iiaoia?ao?? (1997?.), XXIII nan?? iaoeiaeo
iia?aeiieaiue a ?oioi?? (1997?.), eiioa?aioe?? i?enay/ai?e 125-??//th
oaeoeueoaoo ?iaeono??aeueii? o?i?? oi?aa?neoaoo “Iie?oaoi?ea” o
Aooa?ano? (1997?.), o?aoueiio oe?a?inueei-iieuenueeiio neiiic?oi?
“Oai?aoe/ia ? aenia?eiaioaeueia aea/aiiy i?aeiiaa?oiaaeo yaeu oa ?o
oaoiieia?/ia canoinoaaiiy” (1998?.),
Ioae?eaoe??. Ca iaoa??aeaie aeena?oaoe?? iioae?eiaaii 22 ?iaioe, ui
aeeth/athoue 6 noaoae ? 16 iaoa??ae?a oa oac aeiiia?aeae ia
eiioa?aioe?yo.
Iniiai? ?acoeueoaoe, ye? aeiinyoueny ia caoeno:
– aea/aiiy oi?i ?nioaaiiy ?ooai?th(IV) a iaeiiieaenoth/eo na?aaeiaeuao;
– eiiieaeniooai?aiiy ?ooai?th(IV) c oeeo?aoiith, oa?o?aoiith ?
ienaeaoiith eeneioaie a eeneiio oa oeeo?aoiith ? oa?o?aoiith a eoaeiiio
na?aaeiaeuao;
– eaoae?oe/i? i?ioeane a ?ic/eiao ?ooai?th(IV) c iaeei ai?noii ?ooai?th;
– aiae?oe/ia canoinoaaiiy eaoae?oe/iiai aeaeo?iaeiiai i?ioeano.
Iaoiaee aeine?aeaeaiue. Aeena?oaoe?eia ?iaioa aeeiiaia ?c canoinoaaiiyi
eiiieaeno aenia?eiaioaeueieo (aieueoaiia?iiao??y, ?iiiee iai?i.
niaeo?ioioiiao??y) ? oai?aoe/ieo (oa?iiaeeiai?/iee aiae?c) iaoiae?a
aeine?aeaeaiue.
No?oeoo?a ? ia’?i aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny ?c anooio,
ia?ae?eo oiiaieo iicia/aiue ? nei?i/aiue, naie ?icae?e?a, aeniiae?a,
nieneo aeei?enoaieo aeaea?ae ?c 225 ia?iaioaaiue a?o/eciyieo ?
ca?oa?aeieo aaoi??a ? aeiaeaoe?a. Aeena?oaoe?y aeeeaaeaia ia 236
noi??ieao, i?noeoue 45 ?enoie?a, 34 oaaeeoe?; aeiaeaoee ?ici?uai? ia 44
noi??ieao.
INIIAIEE CI?NO ?IAIOE
O anooi? iaa?oioiao?oueny aeooaeuei?noue oaie, ?? iaoeiaa iiaecia,
i?aeoe/ia oe?ii?noue, aecia/a?oueny iaoa aeine?aeaeaiue.
O ia?oiio ?icae?e? aeeeaaeaii e?oa?aoo?i? aeai? i?i oi?ie ?nioaaiiy
?ii?a ?ooai?th(IV), ?ooai?th(III), ?ooai?th(II) a iaeiiieaenoth/eo ?
oei?eaeieo na?aaeiaeuao oa a i?enooiino? aeayeeo i?aai?/ieo niieoe,
i?iaaaeaii iaeyae niaeo?ioioiiao?e/ieo ? aieueoaiia?iiao?e/ieo
oa?aeoa?enoee o?i?/ieo oi?i ?ooai?th, a oaeiae iaaiai?aii iayai? a
e?oa?aoo?? aieueoaiia?iiao?e/i? iaoiaeeee aecia/aiiy ?ooai?th, ?o
ia?aaaae ? iaaeie?ee o ii??aiyii? c ?ioeie iaoiaeaie aecia/aiiy.
O ae?oaiio ?icae?e? iaa?oioiaaii aea?? iaoiae?a aeine?aeaeaiiy.
Iieacaii, ui aieueoaiia?iiao??y c oaeaeeith ?icai?oeith iioaioe?aeo aea?
iiaeeea?noue aeine?aeaeoaaoe oi?ie ?nioaaiiy ?ii?a o ?ic/ei? oa
oa?aeoa?ecoaaoe i?e?iaeo aeaeo?iaeieo i?ioean?a ca o/anoth oeeo o?i?/ieo
oi?i. Aeey aeine?aeaeaiiy oi?i ?nioaaiiy ?ii?a ?ooai?th a i?enooiino?
ieneeeneio canoiniaaii iaoiae ?iiiiai iai?io. Ii?aeiaiiy
aieueoaiia?iiao??? oa ?iiiiai iai?io aeicaiey? aecia/eoe nooi?iue
ieeniaiiy ?iio ?ooai?th a eiiieaen? oa ni?aa?aeiioaiiy
[iaoae]:[e?aaiae].
Aeey ?iiiiai?iiiai aea/aiiy oi?i ?nioaaiiy ?ooai?th a iaeiiieaenoth/eo
?ic/eiao cai?iiiiiaaii iiaee i?aeo?ae aei ?ioa?i?aoaoe?? ?acoeueoao?a
?iiiiai?iiiai aeine?aeaeaiiy a oiiaao ni?a?nioaaiiy iiiiia?ieo ?
iie?ia?ieo oi?i ?ii?a. Aeey a?aooaaiiy iiaeeiaiiy eao?iiiiai?iieeii ye
a?eueiiai ?iio iaoaeo, oae ? iaaiiai eao?iiiiai eiiieaeno (iiiiia?ii? /e
iie?ia?ii? i?e?iaee) cai?iiiiiaaii ocaaaeueiaia ??aiyiiy ?iiiiai iai?io:
, (1)
ca’ycai? ?c nooiaiai iie?ia?ecaoe?? ? /eneii e?aaiae?a a eiiieaenieo
?iiao MpLq /a?ac ?o ia?oe?aeuei? iieuei? /anoee a ?ic/ei?:
(2)
(3)
, yeo oiiaii aecia/eii ye:
(4)
ocaaaeueiaia ??aiyiiy (1) iiaeia ia?aienaoe o aeaeyae?:
. (5)
, yeee ca’ycaiee ?c cia/aiiyie ca?yae?a ie?aieo eiiieaen?a MpLq
ni?aa?aeiioaiiyi:
. (6)
A oiiaao ni?a?nioaaiiy o ?ic/ei? iiiiia?ieo oa iie?ia?ieo oi?i
eiiieaen?a ?ic?aoiao?oueny na?aaei?e eiao?oe??io ?iciiae?eo:
, (7)
??aiyiiyi:
. (8)
iiaea ci?ithaaoenue a iaaeao cia/aiue ca?yae?a iiiiia?ii? ? iie?ia?ii?
oi?i eiiieaen?a MpLq.
A ca’yceo c noia?a/eeaeie e?oa?aoo?ieie aeaieie uiaei oi?i ?nioaaiiy
?ooai?th a aeaeo?ie?oe/ieo na?aaeiaeuao (aiii- ? aaoa?iaaiieo,
eiiieaenoth/eo ? iaeiiieaenoth/eo) o o?aoueiio ?icae?e? i?iaaaeaii
oa?iiaeeiai?/i? ?ic?aooiee no?eeino? ??cieo o?i?/ieo oi?i ?ooai?th. An?
?ic?aooiee i?iaaaeai? c aeei?enoaiiyi oa?iiaeeiai?/ieo eiinoaio c
iaeyaeo J.Rard (Chem.Rev.-1985.-V.85, ?1.- ?.1-39.) ? aacothoueny ia
canoinoaaii? ??aiyiue iaoa??aeueiiai aaeaino a iaaeao iaoiaeo caeeoeiaeo
eiioeaio?aoe?e. A ?acoeueoao? i?iaaaeaieo ?ic?aooie?a anoaiiaeaii
iaeano? oa?iiaeeiai?/ii? no?eeino? RuO2*2H2O(s) ? Ru(OH)3*H2O(s) oa
iaeano? aeii?ioaaiiy ?ic/eiieo o?i?/ieo oi?i Ru(III) ? Ru(IV) (oaae.1).
Oaaeeoey 1.
Iaeano? aeii?ioaaiiy /anoeiie Ru(III) ? Ru(IV) a nenoaiao
iaei?ic/eiiee a?ae?ieneae – iane/aiee ?ic/ei
Nenoaia *anoeiea ?ioa?aae ?I iaeanoae aeii?ioaaiiiy /anoeiie
= 1.0*10-6 iieue/e
Ru(OH)3*H2O(s) 0 F pH F 1.76 1.76 F pH F 2.42 2.42 F pH F 14.0 0 F pH
F 1.76 1.76 F pH F 4.42 4.42 F pH F 14.0
RuO2*2H2O(s) 0 F pH F 1.05 1.05 F pH F 3.93 3.93 F pH F 14.0 0 F pH F
2.55 2.55 F pH F 4.43 4.43 F pH F 14.0
0 F pH F 3.90 3.90 F pH F 10.10 10.10 F pH F 14.0 0 F pH F 4.90 4.90 F
pH F 8.10 8.10 F pH F 14.0
?en. 1. Ae?aa?aia Io?aa aeey nenoaie Ru–H2O i?e NRu =
1*10-4 iieue/e.
Oi?ia ?nioaaiiy ?ii?a Ru(III) ? Ru(IV) caeaaeeoue a?ae eiioeaio?aoe??
?ii?a-e?aaiae?a oa eiinoaio no?eeino? eiiieaenieo ?ii?a. Iaie
?ic?aoiaai? iaeano? aeii?ioaaiiy o?i?/ieo oi?i Ru(III) ? Ru(IV) a
i?enooiino? oei?eae-?ii?a ? iieacaii, ui aeii?ioth/eie oi?iaie caeaaeii
a?ae eiioeaio?aoe?? oei?eae-?iio ? Ru(OH)22+, Ru(OH)2Cl+, Ru(OH)2Cl42-,
Ru3+, RuCl2+, RuCl2+, RuCl3, RuCl4-, RuCl52-, RuCl63- (?I=0). Aeey
aea/aiiy oa?iiaeeiai?/ii? no?eeino? ??cieo o?i?/ieo oi?i ?ooai?th a
?aaeoe?yo aeeni?iii?oe?iioaaiiy iaie iiaoaeiaai? iiaeeo?eiaai? ae?aa?aie
O?inoa aeey nenoai Ru-H2O ? Ru-Cl–H2O aeey CoRu=10-4,10-6 iieue/e i?e
??cieo ?I ? CoCl. C aeaieo ae?aa?ai aeieeaa?, ui no?eeeie nooiaiyie
ieeniaiiy ? +3, +4, a Ru(II) aeeni?iii?oe?iio? ia Ru(0) ? Ru(III) i?e
??cieo cia/aiiyo eeneioiino? ?ic/ei?a oa eiioeaio?aoe?? oei?eae-?iio.
?ooai?e (V) ? ?ooai?e (V?) ? no?eeeie o?i?/ieie oi?iaie i?e ?I
3.00-10.00 oa ?I=13.00 a?aeiia?aeii, a Ru(VII) ? no?eeei aei
aeeni?iii?oe?iioaaiiy i?e ?I?7.00.
Oe?e?nia ea?oeia oa?iiaeeiai?/ieo aeanoeainoae niieoe ?ooai?th a
nenoaiao Ru-H2O ? Ru-Cl–H2O cia?aaeaia ca aeiiiiiaith ae?aa?ai A0-?I ?
A0-lg[Cl-], ye? na?ae/aoue, ui iaea?eueo no?eeith o?i?/iith oi?iith a
nenoai? Ru-H2O ? Ru(IV) (?en.1), a a nenoai? Ru-Cl–H2O ? Ru(III). ?iie
Ru(II) ? oa?iiaeeiai?/ii iano?ee? a onueiio ae?aiacii? ?I ?
CoRu=10-4-10-6 iieue/e, a oaeiae a i?enooiino? oei?eae-?iio.
A /aoaa?oiio ?icae?e? aeena?oaoe?? iaaaaeaii ?acoeueoaoe
aieueoaiia?iiao?e/ieo oa ?iiiiai?iieo aeine?aeaeaiue oi?i ?nioaaiiy
Ru(IV) a iaeiiieaenoth/eo na?aaeiaeuao. Anoaiiaeaii, ui a caeaaeiino?
a?ae eeneioiino? na?aaeiaeua ia aieueoaiia?ia?ai? Ru(IV) ia iao??e
ia?oei?ao? niinoa??aaee ??cio e?euee?noue iiey?ia?ao?/ieo oaeeue: i?e
?I=0.80 Aie =-0.420 A, i?e ?I=1.50 Aie =+0.075 A, Aie =-0.400 A, Aie
=-0.550 A (ian.e.a.). Aeine?aeaeaiiy aeaeo?iaeieo i?ioean?a ca e?eoa???i
I?eieueniia-Oaeia oa iaoeeii aeno?aeii? a?eee aieueoaiia?ia?aie aeaco?
ia iaiai?ioi?e oa?aeoa? an?o aeaeo?iaeieo i?ioean?a, a aea/aiiy i?e?iaee
no?oio ca aeae?eueeiia e?eoa??yie aeaco? ia aeeooc?eio c e?iaoe/ieie
iaiaaeaiiyie, ye? iineeththoueny aeey an?o i?ioean?a ?c ciaioaiiyi
eiioeaio?aoe?? a?ae?iaai-?ii?a o ?ic/ei?. Aeaeo?iaei? i?ioeane c Aie
=+0.075 A ? Aie =-0.550 A i?ioiaeyoue ca o/anoth a?ae?iaai-?ii?a, i?i ui
na?ae/eoue iaoee i?yieo Aie – ?I . ?ic?aooiie oaiaaina eooa iaoeeo
aeno?aeii? a?eee aieueoaiia?ia?aie aeey aeaeo?iaeiiai i?ioeano c Aie
=+0.075 A na?ae/eoue i?i o/anoue a?eueoa iaeiiai aeaeo?iia a
iioaioe?ae-aecia/oaai?e noaae??.
Iaoiaeii ?iiiiai iai?io anoaiiaeai? na?aaei? ca?yaee a?ae?ienieiiieaeno
Ru(IV) a ia?oei?aoieo ?ic/eiao +1.91 (CoRu=1.44*10-4 iieue/e,
?I=1.65-1.78) ? +1.46 (CoRu=2.40*10-4 iieue/e, ?I=1.00) oa na?aaei?e
nooi?iue iie?ia?ecaoe?? a?ae?ienieiiieaen?a Ru(IV) 1.63 (CoRu=10-4?10-5
iieue/e, ?I=1.80). Io?eiai? cia/aiiy na?aaeiueiai nooiaiy iie?ia?ecaoe??
? na?aaeiueiai ca?yaeo a?ae?ienieiiieaen?a Ru(IV) a ia?oei?aoieo
?ic/eiao na?ae/aoue i?i ni?a?nioaaiiy iiiiia?ii? ? oao?aia?ii? oi?i
a?ae?ienieiiieaen?a Ru(IV) (Ru(OH)22+ ? Ru4(OH)124+), ui aeia?a
ocaiaeaeo?oueny c iiaoaeiaaieie a ?icae?e? 3 ae?aa?aiaie aaoa?iaaiieo
o?i?/ieo ??aiiaaa.
Ii?aeiaiiy ?iiiiai?iieo ? aieueoaiia?iiao?e/ieo aeine?aeaeaiue
aeicaiey? iienaoe i?ioean a?aeiiaeaiiy Ru(IV) aei Ru(III) noaiaie:
, (9)
, (10)
, (11)
a a?aeiiaeaiiy ?ii?a Ru(III) aei Ru(II) a?aeiia?aeii:
= -0.400 A
(12)
= -0.550 A:
. (13)
Cai?iiiiiaai? noaie aeia?a ocaiaeaeothoueny c ?acoeueoaoaie ?ic?aooie?a
oa?iiaeeiai?/ii? no?eeino? ??cieo o?i?/ieo oi?i ?ooai?th, ye?
i?aaenoaaeai? ae?aa?aiaie Io?aa a o?aoueiio ?icae?e? aeena?oaoe??
(?en.1).
O i’yoiio ?icae?e? aeena?oaoe?eii? ?iaioe aeeeaaeaii ?acoeueoaoe
aeine?aeaeaiue eiiieaeniooai?aiiy ?ii?a Ru(IV) c oeeo?aoiith ?
oa?o?aoiith ieneeeneioaie oa ienaeaoiith eeneioith. On? eiiieaeni?
niieoee Ru(IV) c ieneeeneioaie ? iaei?ino?oith aeeea?aiiiaith eeneioith
io?eiai? aia?oa, aeei?enoiaoth/e a?ae?ienieiiieaen [Ru(OH)2(H2O)4]2+.
Iaoiaeii ?iiiiai iai?io anoaiiaeaii ni?aa?aeiioaiiy [iaoae]:[e?aaiae] oa
o?i?/io oi?io e?aaiaeo a eiiieaeniiio ?ii?. Cai?iiiiiaai? noaie
eiiieaeniooai?aiiy:
?I=1.80-2.20, NH3Cit:CRu=30?100 : 1
. (14)
?I=1.40-3.30, NH2Tart:CRu=70?1000 : 1
. (15)
pH=1.44-2.44, CH2C2O4:CRu=25?100 : 1
. (16)
Aeine?aeaeai? eiiieaeni? ?iie ?ooai?th(IV) c a?ae?iaaioeeo?ao,
a?ae?iaaioa?o?ao ? ienaeao- ?iiaie iaiai?ioiuei a?aeiiaeththoueny ia
?.e.a. i?e iioaioe?aeao i?eo a?aeiia?aeii +0.014 A, -0.092 A, -0.120 A
(ian.e.a.); aeaeo?iaei? i?ioeane ia oneeaaeiai? o/anoth a?ae?iaai-?ii?a,
ye o aeiaaeeo a?ae?ienieiiieaen?a Ru(IV).
A oeeo?aoieo ?ic/eiao c ?I=8.0-12.0 ooai?th?oueny eiiieaeniee ?ii, yeee
ia? a aani?aoe?eiiio niaeo?? iaeneioi iiaeeiaiiy i?e 540 ii. Oea,
i/aaeaeii, ci?oa-iiaaeaioiee ?ii Ru(IV, III) iie?ia?ii? i?e?iaee, yeee
a?aeiiaeth?oueny i?e -0.570 A (ian.e.a.). Iaea?aeaiee aia?oa
a?ae?iaaioa?o?aoiee eiiieaen Ru(IV) ia? a aani?aoe?eiiio niaeo??
iaeneioi iiaeeiaiiy i?e 490 ii. A eoaeieo oa?o?aoieo ?ic/eiao (?I>8.0)
ooai?th?oueny eiiieaeniee ?ii c iaeneioiii iiaeeiaiiy i?e 715 ii, yeee
a?aeiiaeth?oueny i?e -0.300 A. Iiaeeeai, a?i oaeiae ? iie?ia?ii?
i?e?iaee. A neaaeieeneeo ? eoaeieo ?ic/eiao (?I>4.0) ienaeaoiee eiiieaen
Ru(IV) ?oeio?oueny c ooai?aiiyi a?ae?aoiaaiiai ieneaeo RuO2*2H2O.
O oinoiio ?icae?e? iienai? ?acoeueoaoe aieueoaiia?iiao?e/ieo
aeine?aeaeaiue eaoae?oe/ieo i?ioean?a a nenoai? Ru(IV)+ClO4- a ?ic/eiao
c iaeei ai?noii ?ooai?th(IV). Anoaiiaeaii, ui a caeaaeiino? a?ae
eeneioiino? ?ic/ei?a ia aieueoaiia?ia?ai? ia?oei?aoiiai ?ic/eio Ru(IV)
niinoa??aa?oueny aea? iiey?ia?ao?/i? oaee? c Ai1e =-0.970 A ? Ai2e
=-1.240 A (?en.2).
Iaeaeaa aeaeo?iaei? i?ioeane ? iaiai?ioi?. Ae?oaee aeaeo?iaeiee i?ioean
oa?aeoa?eco?oueny iayai?noth a?noa?acenii? iaoe? ia aieueoaiia?ia?ai?:
i?e cai?ioi?e ?icai?ooe? iioaioe?aeo niinoa??aa?oueny no?eaeiiiae?aia
c?inoaiiy no?oio ca cia/aiiyi aeuei a?ae eaoiaeiiai no?oio i?e iaeieo ?
oeo aea cia/aiiyo iai?oae. ?c ca?eueoaiiyi eiioeaio?aoe?? oiiiaiai
aeaeo?ie?oo (c?inoaiiy ?iiii? neee ?ic/eio) aenioa ae?oai? oaee? ?noioii
ciaioo?oueny. Aenioa oaee? c Ai2e =-1.240 A ciaioo?oueny oaeiae ?c
ciaioaiiyi eiioeaio?aoe?? a?ae?iaai-?ii?a a ?ic/ei? ? cieeiaiiy i?eo
niinoa??aa?oueny i?e ?I>2.0. Ioaea, oeae aeaeo?iaeiee i?ioean ?
aaoieaoae?oe/iei aeaeo?iaeiei i?ioeanii, iia’ycaiei c aeae?eaiiyi
aiaeith ia aeaye?e aeoeai?e oi?i? ?ooai?th ?c nooiaiai ieeniaiiy
“ioeue”.
?en.2. Aieueoaiia?ia e?eaa Ru(IV) ia iao??e ia?oei?ao?: 1 – e?eaa oiio
0.25 iieue/e NaClO4, ?I = 1.5; 2 – e?eaa 3.50*10-5 iieue/e Ru(IV),
?I = 1.5 ia oii? 0.25 iieue/e NaClO4.
~10-6 iieue/e. ?o aeii?ioaaiiy o aeacaiiio ?ioa?aae? ?I caaacia/o?
o/anoue a aeaeo?iaeiiio i?ioean? c Aie =-0.970 A iaei??? ? oi? ae
e?eueeino? aeaeo?iaeoeaieo /anoeiie.
Aeniea cia/aiiy aaee/eie no?oio aeey i?eo c Aie =-0.970 A aeaco? ia
eaoae?oe/io i?e?iaeo i?ioeano, yeee, ca?aeii e?eoa??th
I?eieueniia-Oaeia, iaeaaeeoue aei eaoae?oe/ieo c iaiai?ioi?i
ia?aianaiiyi aeaeo?ii?a, ca yeei eaea o?i?/ia ?aaeoe?y. Aeine?aeaeaiiy
i?e?iaee no?oio i?iaaaeaia ca aeae?eueeiia e?eoa??yie: lg Iie – lgu, Iie
– u1/2 ? oaiia?aoo?iith caeaaei?noth neee no?oio aeaco? ia iayai?noue
iiia?aaeiuei? o?i?/ii? ?aaeoe??. I?i oea ae na?ae/eoue aeniea cia/aiiy
oaiia?aoo?iiai eiao?oe??ioo no?oio 5.58%/E. Ioaea, aeine?aeaeoaaiee
aeaeo?iaeiee i?ioean ? eaoae?oe/iei c iaiai?ioi?i ia?aianaiiyi
aeaeo?ii?a c iiia?aaeiueith ? ianooiiith o?i?/ieie ?aaeoe?yie.
= 0.25 iieue/e.
Aaaaeaiiy ieneeeneio a iiey?ia?ao?/iee oii i?eaiaeeoue aei iie?auaiiy
oi?ie aieueoaiia?ii? e?eai? i?e Aie =-0.970 A, yea iicia/a?oueny ia
cieeiaii? ia?aaeio ia aeno?aei?e aieueoaiia?ia?aie, a oaeiae ?iaeoue
iiaeeeaei aei??thaaiiy aiae?oe/iiai ne-aiaeo a oe?ieiio ae?aiacii? ?I
1.0-6.0, oiae? ye a ia?oei?aoieo ?ic/eiao eeoa aei ?I 4.0. A i?enooiino?
ienaeaoii? eeneioe oi?ia aieueoaiia?ia?aie caeeoa?oueny iaci?iiith.
C?inoaiiy eiioeaio?aoe?? ieneeeneio oa ienaeaoii? eeneioe a
iiey?ia?ao?/iiio oii? nii/aoeo ca?eueoo? aaee/eio aiae?oe/iiai neaiaeo,
a i?e aenieeo ai?noao ?o a ?ic/ei? (H2C2O4 a?eueoa 100-e?aoiiai, H3Cit
a?eueoa 1000-e?aoiiai, H2Tart a?eueoa 500-e?aoiiai) ciaioo? aaee/eio
neee no?oio. C?inoaiiy neee no?oio iia’ycaia c ia?aaaaeaiiyi ??cieo
o?i?/ieo oi?i Ru(IV) o a?aeiia?aei? iiey?ia?ao?/iiaeoeai? eiiieaeni?
?iie, a ianooiia ciaioaiiy – c ooai?aiiyi eiiieaenieo ?ii?a c aeuei
eii?aeeiaoe?eiei /eneii, ye?, i/aaeaeii, iathoue ?ioo iiey?ia?ao?/io
aeoeai?noue. Aianaiiy a ?ic/ei ieneeeneio ? ienaeaoii? eeneioe ia
ci?ith? caeaaei?noue Aie – ?I. Caeaaei?noue Iie-?I a ?ic/eiao ieneeeneio
caa??aa? e?i?eio ae?eyieo a ae?aiacii? ?I 1.5-2.5 ? 1.5-2.0 aeey
oeeo?aoii? ? oa?o?aoii? eeneio a?aeiia?aeii, a a i?enooiino? ienaeaoii?
eeneioe neea no?oio ciaioo?oueny ?c ciaioaiiyi eiioeaio?aoe??
a?ae?iaai-?ii?a a ?ic/ei?.
Iaoai?ci aeaeo?iaeiiai i?ioeano a i?enooiino? ieneeeneio ? ienaeaoii?
eeneioe, ca eeaneo?eaoe??th I?eieueniia-Oaeia, a?aeiia?aea? oeio VIII,
oiaoi i?ioiaeeoue eaoae?oe/ia ?aaeoe?y c iaiai?ioi?i ia?aianaiiyi
aeaeo?ii?a. I?e?iaea no?oio aeaeo?iaeiiai i?ioeano a i?enooiino?
ieneeeneio caeeoa?oueny aeeooc?eiith c e?iaoe/ieie iaiaaeaiiyie.
Aeaeo?iaeiiio i?ioeano ia?aaeo? o?i?/ia ?aaeoe?y, i?i ui na?ae/eoue
aeniea cia/aiiy oaiia?aoo?iiai eiao?oe??ioo no?oio: 5.18 %/E a
ia?oei?aoii-oeeo?aoieo, 5.25 %/E a ia?oei?aoii-oa?o?aoieo, 6.83 %/E a
ia?oei?aoii-ienaeaoieo ?ic/eiao.
I?enooi?noue oei?eae- ? i?o?ao-?ii?a ca?eueoo? aaee/eio aiae?oe/iiai
neaiaeo i?e Aie =-0.970 A. Aea, yeui a i?enooiino? oei?eae-?iio ?c
ciaioaiiyi eeneioiino? ?ic/ei?a neea no?oio iinooiiai ciaioo?oueny, oi a
i?enooiino? i?o?ao-?iio niinoa??aa?oueny ai?eciioaeueia e?i?eia ae?eyiea
no?oio, iiae?aii ye o ia?oei?aoieo ?ic/eiao (?en.3). Aeine?aeaeaiiy
aieeao eiioeaio?aoe?? oeeo ?ii?a oa eeneioiino? ?ic/ei?a ia aaee/eio
aiae?oe/iiai neaiaeo iieacothoue, ui o aeiaaeeo oei?eae-?iio i?aeaeuaiiy
aaee/eie no?oio aeeeeeaia ooai?aiiyi o?i?/ieo oi?i Ru(IV): Ru(OH)2Cl42-
? Ru(III): RuCl52-, RuCl63-. Aieea i?o?ao-?iio, i/aaeaeii, iia’ycaiee ?c
eaoae?cii ai?iiii-ieenieeii.
Ocaaaeueithth/e aenia?eiaioaeuei? ?acoeueoaoe iaie cai?iiiiiaaia
ianooiia noaia eaoae?oe/iiai aeaeo?iaeiiai i?ioeano:
O nueiiiio ?icae?e? ?icaeyiooi aiae?oe/ia canoinoaaiiy aeine?aeaeaiiai
a ?icae?e? 6 eaoae?oe/iiai aeaeo?iaeiiai i?ioeano i?e Aie =-0.970 A.
Iieacaii, ui eaoae?oe/ia oaeey ?ooai?th c Aie =-0.970 A iiaea
canoiniaoaaoenue aeey aecia/aiiy ai?noo ?ooai?th i?e oaeeo oiiaao
iiey?ia?aooaaiiy: Aii/. = -0.400 A, DA = 0.700 A, tc=3 n, n = 0.5 A/n.
Anoaiiaeaii, ui a iioeiaeueieo oiiaao iiey?ia?aooaaiiy (0.25
iieue/eNaClO4+2.50*10-2iieue/e H3Cit, pH=1.50) a iaaeao eiioeaio?aoe??
?ooai?th 1.00*10-6 – 3.50*10-5 iieue/e niinoa??aa?oueny e?i?eia
caeaaei?noue, yea iieno?oueny ??aiyiiyi:
?ie =0.001+0.45NRu,
aea ?ie – aei??thaaia cia/aiiy eaoiaeiiai no?oio, ieA;
NRu – eiioeaio?aoe?y ?ooai?th a aeine?aeaeoaaiiio ?ic/ei?,
ieiieue/e.
Eiao?oe??io ei?aeyoe?? noaiiaeoue 0.99, aeenia?n?y a?ao?ea S2=0.02,
ieaeiy iaaea aeyaeaiiy 5.00*10-7 iieue/e.
Iaie aeine?aeaeaii aieea 18 noi?iii?o ?ii?a ia aieueoaiia?iiao?e/ia
aecia/aiiy ?ooai?th. Anoaiiaeaii, ui Bi(III), Zn(II), Cr(VI) i?e 5 –
e?aoiiio, Pt(IV) i?e 10 – e?aoiiio, BrO3- i?e 50 – e?aoiiio, Mn(II),
Fe(II), Cu(II), Ni(II), Pd(II), Cd(II) i?e n*102 – e?aoiiio, a Al(III),
Pb(II), Ca(II), Mg(II), Br-, NO3-, SO42- i?e n*103 – e?aoiiio ai?no? ia
caaaaeathoue aecia/aiith ?ooai?th. Ca?aeii cai?iiiiiaai? iaie iaoiaeeee
aieueoaiia?iiao?e/iiai aecia/aiiy ?ooai?th, i?iaaaeaii aiae?c
iai?ai?ia?aeieeiaeo iano, ?acoeueoaoe yeiai i?aaenoaaeai? a oaae.2.
Oaaeeoey 2.
Ai?no ?ooai?th a iai?i?ia?aeieeiaeo ianoao (n = 5, P = 0.95)
miaa., a aieueoaiia?iiao?e/iee niaeo?ioioiiao?e/iee
Ai?no Ru, % Sr Ai?no Ru, % Sr
0.5004 0.25±0.01 0.032 0.24±0.02 0.067
0.2503 0.25±0.02 0.061 0.25±0.03 0.097
0.4894 0.24±0.02 0.062 0.24±0.03 0.101
0.5010+0.0054Ru 0.24±0.02 0.062 0.25±0.03 0.097
0.2012 0.50±0.02 0.032 0.52±0.02 0.031
0.3135 0.49±0.02 0.033 0.51±0.03 0.047
0.2108+0.0039Ru 0.49±0.02 0.033 0.51±0.03 0.047
0.0109 4.24±0.21 0.040 4.29±0.25 0.047
0.0250 4.20±0.20 0.038 4.28±0.29 0.055
0.0102+0.0011Ru 4.22±0.20 0.038 4.27±0.30 0.057
0.0101 29.80±0.31 0.010 ia aiae?coaaee
0.0085+0.0018Ru 29.58±0.35 0.012 ia aiae?coaaee
I?aaeeuei?noue aieueoaiia?iiao?e/iiai aecia/aiiy ia?aa??yee
niaeo?ioioiiao?e/iei iaoiaeii. Aeecuee?noue io?eiaieo ?acoeueoao?a i?ae
ia?aeaeueieie i?iaaie, iaaaeeea ??cieoey a iaae?eiiio ?ioa?aae?
i?aeoaa?aeaeothoue i?aaeeuei?noue aieueoaiia?iiao?e/iiai aecia/aiiy.
Aecia/aiiy ai?noo ?ooai?th a ianoao a i?enooiino? aeiaaaee iaoae?/iiai
?ooai?th aeiaiaeeoue, ui ?ooai?e ia ao?a/a?oueny i?e nieaaeyii? c
ieenithaaeueiith noi?ooth. Aeaui iaio? cia/aiiy noaiaea?oiiai
a?aeoeeaiiy aeey aieueoaiia?iiao?e/iiai aecia/aiiy, ii??aiyii ?c
niaeo?ioioiiao?e/iei, na?ae/aoue i?i e?auo a?aeoai?thaai?noue
aieueoaiia?iiao?e/ii? iaoiaeeee. E??i oiai, niaeo?ioioiiao?e/ia
iaoiaeeea ia aeicaiey? aiae?coaaoe ianoe c aaeeeei ai?noii Oa?oio, oiae?
ye aieueoaiia?iiao?e/ia ? cia/ii naeaeoeai?oa.
?ic?iaeaia iaoiaeeea aecia/aiiy ai?noo ?ooai?th a nieaaao nenoai
Nd-Ru-Mn-Si, Ho-Ru-Ga, Ce-Ru-Ga. Anoaiiaeaii, ui aeey ia?aaaaeaiiy
eiiiiiaio?a nieaao a ?ic/ei iaiao?aeia nieaaeyiiy c ieenithaaeueiith
noi?ooth. ?iie Nd(III), Ce(IV), Mn(II), Ga(III) ? Ho(III) ia
caaaaeathoue aecia/aiith ?ooai?th a iioeiaeueieo oiiaao
iiey?ia?aooaaiiy. sse aeaeii c oaae.3, io?eiai? c ??cieo iaaaaeie
na?aaei? ?acoeueoaoe aeecuee?, ??cieoey a iaae?eiiio ?ioa?aae? iaaaeeea,
ui i?aeoaa?aeaeo? i?aaeeuei?noue io?eiaieo ?acoeueoao?a.
?ic?iaeaia iaie iaoiaeeea aieueoaiia?iiao?e/iiai aecia/aiiy ?ooai?th ?
aeni?ania, i?inoa ? iaae?eia; ?e aeanoeaa iecueea iaaea aeyaeaiiy
(5.00*10-7 iieue/e) ? oe?ieee ?ioa?aae e?i?eiino? (1.00*10-6 – 3.50*10-5
iieue/e) ? ia aeiaaa? a?aeae?eaiiy aaaaoueio noi?iii?o ?ii?a.
Aieueoaiia?iiao?e/ia iaoiaeeea aecia/aiiy ?ooai?th aoanoiaaia oa ?
ai?iaaaeaeaia a aiae?oe/ieo eaai?aoi??yo AeC “EI?OA” ? OcIA
iaoeiai-aeine?aeiiai ?inoeoooo “Iiinoa?a”.
Oaaeeoey 3.
Aecia/aiiy ai?noo ?ooai?th a nieaaao (n = 5, P = 0.95)
Neeaae nieaao miaa., a Ai?no Ru, ian. % Ciaeaeaii Ru, ian. % Sr
Ce27Ru10Ga63 0.1149 11.00 10.89±0.38 0.028
0.0153+0.0021 a Ru 10.82±0.40 0.030
Ho25Ru4Ga71 0.2583 4.27 4.12±0.15 0.030
0.0231+0.0017 a Ru 4.12±0.11 0.021
Nd20Mn8Ru12Si60 0.0415 19.49 19.05±0.42 0.018
0.0538 19.15±0.48 0.020
Nd33.3Mn13.3Ru46.7Si6.7 0.0786 45.20 44.80±0.61 0.011
0.0310 44.68±0.65 0.012
Nd15Ru42.5Si42.5 0.0158 56.13 55.02±0.93 0.014
0.0136 54.89±0.97 0.014
AENIIAEE
1. C iaeyaeo e?oa?aoo?e aeieeaa?, ui aeooaeueiith caeeoa?oueny ?ic?iaea
aeniei/ooeeaeo, naeaeoeaieo, oi/ieo iaoiaeee aecia/aiiy Ru, ye?
caaacia/oaaee a aenieo a?aeoai?thaai?noue ?acoeueoao?a aiae?co. Oiio
aaaeeeaei ? io?eiaiiy ?ii?a ?ooai?th a iaei?e o?i?/i?e oi?i?, ooai?aiiy
yei? iiaeooue caaacia/oaaoe ieneeeneioe. Niieoee ?ooai?th c
ieneeeneioaie iaeiaea/ai? ? ? ia?niaeoeaiei ia’?eoii aeine?aeaeaiiy c
iaoith ?o ianooiiiai canoinoaaiiy a aiae?c?.
2. Aia?oa i?iaaaeaii aiae?c oa?iiaeeiai?/ii? no?eeino? ??cieo o?i?/ieo
oi?i ?ooai?th, anoaiiaeai? iaae? aeii?ioaaiiy iiiiia?ieo ? oao?aia?ieo
oi?i Ru(IV), aeine?aeaeai? oiiae no?eeino? a?ae?ieneae?a Ru(IV) ?
Ru(III), iiaoaeiaai? iiaeeo?eiaai? ae?aa?aie O?inoa ? ae?aa?aie Io?aa.
.
o?i?/ieo oi?i ?ooai?th(IV).
5. Aeine?aeaeaii aieueoaiia?i? oa?aeoa?enoeee ?ii?a ?ooai?th (IV) a
ia?oei?aoieo ?ic/eiao. Anoaiiaeaii, ui i?ioean a?aeiiaeaiiy
a?ae?ienieiiieaen?a Ru(IV) ia ?.e.a. a neaaieeneeo ?ic/eiao ia?
iaiai?ioi?e oa?aeoa?, a i?e?iaea no?oio – aeeooc?eia. Cai?iiiiiaaii
noaie a?aeiiaeaiiy iiiiia?ii? ? oao?aia?ii? oi?i Ru(IV) a caeaaeiino?
a?ae ?I ?ic/ei?a.
6. Aea/aii oa?aeoa? i?ioeano ? i?e?iaeo no?oio a?aeiiaeaiiy ?ii?a
Ru(III), ye? ooai?ththoueny a ?acoeueoao? a?aeiiaeaiiy ?ii?a Ru(IV).
Iieacaii, ui a caeaaeiino? a?ae eeneioiino? ?ic/ei?a ?iie Ru(III)
iiaeooue ?nioaaoe o aeaio o?i?/ieo oi?iao, a?aeiiaeaiiy yeeo ia ?.e.a.
a?aeaoaa?oueny iine?aeiaii i?e Aie= -0.400 A ? i?e Aie = -0.550 A.
7. Aia?oa aeine?aeaeaii eiiieaeniooai?aiiy ?ooai?th(IV) c oeeo?aoiith,
oa?o?aoiith ? ienaeaoiith eeneioaie. Iaoiaeii ?iiiiai iai?io anoaiiaeaii
ni?aa?aeiioaiiy [iaoae] : [e?aaiae] oa o?i?/io oi?io e?aaiaeo.
Cai?iiiiiaai? noaie eiiieaeniooai?aiiy. Aeey anoaiiaeaieo o?i?/ieo oi?i
eiiieaenieo ?ii?a: [Ru(C6H6O7)2(OH)x(H2O)2-x]-x,
[Ru(C2O4)2(OH)x(H2O)2-x]-x, [Ru(C4H5O6)(OH)x(H2O)5-x]3-x aea/ai? aeaye?
niaeo?ioioiiao?e/i? oa aieueoaiia?iiao?e/i? oa?aeoa?enoeee.
8. Aia?oa anoaiiaeaii ooai?aiiy eiiieaenieo niieoe ?ooai?th (IV) c
oeeo?ao- ? oa?o?ao-?iiaie a eoaeieo ?ic/eiao (?I > 8.0). Aeneiaeaii
i?eiouaiiy, ui eiiieaeniee ?ii ?ooai?th c oeeo?ao-?iiii i?noeoue ?ooai?e
?c nooiaiyie ieeniaiiy +3 ? +4 ?, i/aaeaeii, ? a?yaea?iee; eiiieaeniee
?ii ?ooai?th c oa?o?ao-?iiii i?noeoue ?ooai?e ?c nooiaiai ieeniaiiy +4 ?
? iie?ia?ii? i?e?iaee. Anoaiiaeaii, ui ienaeao-?ii ia ooai?th?
eiiieaenieo niieoe c Ru(IV) a neaaieeneeo (?I > 4.00) ? eoaeieo
?ic/eiao.
= -1.240 A ? aaoieaoae?oe/iei.
10. ?ic?iaeaia aieueoaiia?iiao?e/ia iaoiaeeea aecia/aiiy ?ooai?th, yea
aea? iiaeeea?noue aecia/aoe eiioeaio?aoe?th ?ooai?th a iaaeao 3.50*10-5
? 1.00*10-6 iieue/e; ieaeiy iaaea aeyaeaiiy noaiiaeoue 5.00*10-7
iieue/e. Aeine?aeaeaii aieea 18 ?ii?a ia aieueoaiia?iiao?e/ia aecia/aiiy
?ooai?th. ?ic?iaeaia iaoiaeeea aeei?enoaia aeey aiae?co nieaa?a ?
iai?ai?ia?aeieeiaeo iano.
Nienie ioae?eaoe?e
1.A?oaeaaneay O.ss., A?iineay E.A. Oioiiao?e/aneia ii?aaeaeaiea ?ooaiey
a i?enoonoaee eiiia aeaeaca a neiaeiuo iauaeoao.// Caaiae. eaai?aoi?ey.
– 1995. – O.61, ?12. – N.4-5.
2. A?oaeaanueea O.ss., A?iinueea E.A. O?iiiaiia?iiao?e/ia aeine?aeaeaiiy
e?iaoeee eiiieaeniooai?aiiy ?ooai?th (IV) a ?ic/eiao ieneeeneio.// Iaoe.
aeii. Anaoe?. eiio. c aiae?o. o?i??, 18-21 aa?aniy 1995 ?.- Ee?a, 1995.
– N.72.
3. A?oaeaanueea O.ss., A?iinueea E.A., Aeoaea? ?.I. Aieueoaiia?iiao?e/ia
aeine?aeaeaiiy aeoeaiino? ?ii?a ?ooai?th (IV) a ?ic/eiao ieneeeneio.//
Oace aeii. iaoe.-i?aeo. eiio. “Euea?anuee? o?i?/i? /eoaiiy”, 26 o?aaiy
1995 ?. – Euea?a, 1995. – N.145.
4. Vrublevska T.Ya., Vronska L.V., Lobojko V.S. Chronoamperemetric
analysis of complex semiconductor compositions on platinum metals
contents.// Abstract booklet intern. school-confer. “Physical problems
in material science of semiconductors”, 11th-16th of September, 1995.-
Chernivtsi, Ukraine, 1995. – P.115.
5. A?oaeaanueea O.ss., A?iinueea E.A., Aeoaea? ?.I.
Inoeeeiiiey?ia?ao?/ia aecia/aiiy ai?noo ?ooai?th a nieaaao nenoai
Nd-Ru-Si, Nd-Ru-Mn-Si.// A?ni. Euea?a. oi-oo. Na?. o?i. – 1996. – A.36.
– N.96-98.
6. A?iinueea E.A. Aieueoaiia?iiao?e/ia aeine?aeaeaiiy oei?eaeieo
eiiieaen?a ?ooai?th caeaaeii a?ae eeneioiino? na?aaeiaeua.// A?ni.
Euea?a. oi-oo. Na?. o?i.-1996.- A.36.- N.96-98.
7. A?iinueea E.A., A?oaeaanueea O.ss., Nei?iaaaaoee ss.I.
O?iiiaiia?iiao?e/ia aeine?aeaeaiiy e?iaoeee ?ic?yaeo-?ii?caoe?? ?ii?a
Ru(IV) a ?ic/eiao ClO4-+H2C2O4.// Iaoa?. eiio. i?io.-aeee. neeaaeo ?
ani. Euea?a. eiia?oe. aeaaeai??. – Euea?a, 1996.- N.106.
8. A?iinueea E.A., A?oaeaanueea O.ss. Aieueoaiia?iiao??y ?ooai?th (IV) a
i?enooiino? ieneeeneio.// Ca. iaoe. i?aoeue oinoi? iaoe. eiio.
“Euea?anuee? o?i?/i? /eoaiiy” 29-30 o?aaiy 1997. – Euea?a, 1997. – N.72.
9. A?iinueea E.A., A?oaeaanueea O.ss., Nieiaae I.?., Oeiiooe I.N.
Ni?aoe?y ?ooai?th (IV) ?c ia?oei?aoieo ?ic/ei?a i?e?iaeieie ?
neioaoe/ieie ni?aaioaie.// I?aoe? I Cao?aeii-oe?a?i. neiiic?oio c
aaeni?aoe?? oa o?iiaoia?ao??. – Euea?a, 1997 ?. – N.101-102.
10. A?oaeaaneay O.ss., A?iineay E.A., A?oai A.A. Aieueoaiia?iiao?e/aneia
ii?aaeaeaiea ?ooaiey a i?enoonoaee eiiia aeaeaca e ae?oaeo
niioonoaothueo yeaiaioia a neiaeiuo i?aaii-iaoaeee/aneeo eiiiiceoeeyo.//
AEo?i. aiaeeo.oeiee.-1997.- O.52, ?4. – N.418-421.
11. A?oaeaaneay O.ss., A?iineay E.A., Eaaaaeeiaoe E.A.
Aieueoaiia?iiao?e/aneia ii?aaeaeaiea ieaoeiiauo iaoaeeia a neiaeiuo
iieoi?iaiaeieeiauo eiiiiceoeeyo.// Caaiae. eaai?aoi?ey.- 1997. – O.63,
?9. – N.12-14.
12. Povar I., Vronska L., Vrublevska T. Reprezentarea grafica a
echilibretor complexe cu ruteniu: I. Caiculul domeniului de stabilitate
termodinamica a hidroxizilor puthin solubili a Ru(III) si Ru(IV).//
Lucrarile conf. ”Conferintha de chimie ?i inginerie chimica”.
Bucure?ti, 16-18 octombrie 1997.- V.III. – S. 4.83-4.87.
13. Povar I., Vronska L., Vrublevska T. Reprezentarea grafica a
echilibretor complexe cu ruteniu: II. Diagramele de distributie a
speciilor chimie ale Ru(III) si Ru(IV) in sisteme hidrolitice eterogene
hidroxid puthin solubil – solutie saturata.// Lucrarile conf.
”Conferintha de chimie ?i inginerie chimica”. Bucure?ti, 16-18
octombrie 1997.- V.III. – S. 4.88-4.93.
14. Povar I., Vronska L., Vrublevska T. Reprezentarea grafica a
echilibretor complexe cu ruteniu: III. Calculul conditiilor de
disproportionare a Ru in diferite stari de valenta.// Lucrarile conf.
”Conferintha de chimie ?i inginerie chimica”. Bucure?ti, 16-18
octombrie 1997.- V.III. – S. 4.94-4.99.
15. Povar I., Vronska L., Vrublevska T. Reprezentarea grafica a
echilibretor complexe cu ruteniu: IV. Diagramele Pourbaix pentru
sistemul Ru-H2O. // Lucrarile conf. ”Conferintha de chimie ?i inginerie
chimica”. Bucure?ti, 16-18 octombrie 1997.- V.III. – S. 4.100-4.105.
16. Povar I., Vronska L., Vrublevska T. Reprezentarea grafica a
echilibretor complexe cu ruteniu: V. Diagramele potential-pCl pentru
sistemul Ru-Cl–H2O. // Lucrarile conf. ”Conferintha de chimie ?i
inginerie chimica”. Bucure?ti, 16-18 octombrie 1997.- V.III. – S.
4.106-4.109.
17. A?iinueea E.A., A?oaeaanueea O.ss., Iiaa? ?.A. Aeei?enoaiiy
oa?iiaeeiai?/ieo ?ic?aooie?a aeey i?iaiicoaaiiy ?aaeoe?e
aeeni?iii?oe?iioaaiiy a nenoai? Ru-Cl-H2O.// A?ni. aea?ae. oi-oo
“Euea?anueea iie?oaoi?ea”. O?i?y, oaoiieia?y ?a/iaei oa ?o
canoinoaaiiy.- 1997. – ?332.- N.39-42.
18. Povar I., Vronska L., Vrublevska T. Considerathii privid calculul
produsului de solubilitate al hidroxizilor puthin solubili din valoarea
pH-ului soluthiei saturate.// Rez. a XXIII-A sesiune de comun. ?tiinth.,
8-10 octombrie 1997. – Caciulata-Valcea, 1997. – S.44.
19. A?iinueea E.A., A?oaeaanueea O.ss., Nieiaae I.?., Oeiiooe I.N.
Eiiieaeniooai?aiiy ?ooai?th a ?ic/eiao ieneeeneio.// Oace aeii. Anaoe?.
eiio. c aiae?o. o?i??. 15-17 aa?aniy 1998?. – Oaeai?iae, 1998. – N.34.
20. A?iinueea E.A., Iiaa? ?.A., A?oaeaanueea O.ss. ?iiiee iai?i o
aeine?aeaeaiiyo iie?ia?ecaoe?? ?ooai?th (IV).// Oace aeii. Anaoe?. eiio.
c aiae?o. o?i??. 15-17 aa?aniy 1998?. – Oaeai?iae, 1998. – N.35.
21. A?oaeaanueea O.ss., A?iinueea E.A., Ei?eoia I.ss. Eiioeaio?oaaiiy oa
?icae?eaiiy iaoae?a ieaoeiiai? a?oie i?e?iaeieie ni?aaioaie.// Oace
aeii. Anaoe?. eiio. c aiae?o. o?i??, 15-17 aa?aniy 1998 ?. – Oaeai?iae,
1998. – N.99.
22. Vrublevska T.Ya., Vronska L.V., Korkuna O.Ya., Matviychuk N.M.
Adsorbion concentration of platinum metals by clynoptilolite.//
Abstracts 3rd Polish-Ukrainian simposium “Theoretical and experimental
studies of interfacial phenomena and their technological application”,
22-24 September 1998. – Lviv, Ukraine, 1998. – P.75.
AIIOAOe?ss
A?iinueea E.A. Aieueoaiia?iiao??y Ru(IV) a i?enooiino? ieneeeneio oa ??
canoinoaaiiy a aiae?c?. – ?oeiien.
Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe
ca niaoe?aeuei?noth 02.00.02. – aiae?oe/ia o?i?y. – Oe?a?inueeee
aea?aeaaiee o?i?ei-oaoiieia?/iee oi?aa?neoao, Aei?i?iiao?ianuee, 1999.
Aeena?oaoe?th i?enay/aii aeine?aeaeaiith i?ioeano eiiieaeniooai?aiiy
?ii?a Ru(IV) c ieneeeneioaie oa eiai canoinoaaiith i?e
aieueoaia?iiao?e/iiio aecia/aii?. Cai?iiiiiaaii noaie eiiieaeniooai?aiiy
?ii?a Ru(IV) c oeeo?aoiith, oa?o?aoiith ? ienaeaoiith eeneioaie. Aia?oa
aeine?aeaeaii iiey?ia?ao?/i? eaoae?oe/i? aoaeoe a ?ic/eiao c iaeei
ai?noii ?ooai?th a i?enooiino? ieneeeneio. Cai?iiiiiaaia noaia
eaoae?oe/iiai aeaeo?iaeiiai i?ioeano. Iieacaia iiaeeea?noue aeei?enoaiiy
oeeo?aoii? eeneioe a yeino? aeiaaaee aei iiey?ia?ao?/iiai oiio, yea
caaacia/o? ooai?aiiy iaei??? aiae?oe/ii? oi?ie ?iio. ?ic?iaeaia /ooeeaa,
naeaeoeaia iaoiaeeea aieueoaiia?iiao?e/iiai aecia/aiiy ?ooai?th a
iai?ai?ia?aeieeiaeo ianoao ? nieaaao.
?acoeueoaoe aeine?aeaeaiue iiaeooue aooe aacith aeey iiooeo ?ioeo
niieoe ?ooai?th c i?aai?/ieie e?aaiaeaie oa ?ic?iaee iiaeo iaoiaeee
aecia/aiiy.
Eeth/ia? neiaa: eiiieaeniooai?aiiy, ieneeeneioe, iiey?ia?ao?/iee
eaoae?oe/iee aoaeo, aieueoaiia?iiao?e/ia aecia/aiiy, iai?a?ia?aeieeiaa
ianoa, nieaa.
SUMMARY
Vrons’ka L.V. Volammetry of Ru(IV) in the presence of oxiacids and its
application in analysis. – Manuscript.
Thesis for obtaining the scientific olegree of Candidate of Chemical
Sciences. Speciality 02.00.02 – analytical chemistry. Ukrainian State
chemical-technologycal University. Dnipropetrovsk, 1999.
Thesis is devoted to investigation of the complexation of the Ru(IV)
ions with oxyacids and their application for volammetric determination.
The schemes of complexation processes of the Ru(IV) with citric,
tartratic and oxalic acids have been proposed. Polarographic catalytic
effects in solutions with low ruthenium content in the presence of
oxyacids have been studied for the first time. The scheme of catalytic
electrode process has been proposed. It has been demonstrated the
possibility of using of citric acid as addition reagent to polarographic
background, which assists in forming the only one analytical form of
ruthenium ion. Sensitive, selective and express method of voltammetric
determination of ruthenium in semiconductive pastes and alloys has been
elaborated.
The results of present investigations can be used as the base for
search of the other ruthenium compounds with organic ligands and
elaboration of nev methods of analysis.
Keywords: complexation, oxyacids, catalytic effect, voltammetric
determination, paste, alloy, sensitivity, selectivity.
AIIIOAOeEss
A?iinea E.A. Aieueoaiia?iiao?ey Ru(IV) a i?enoonoaee ieneeeneio e aa
eniieueciaaiea a aiaeeca. – ?oeiienue.
Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe
ii niaoeeaeueiinoe 02.00.02. – aiaeeoe/aneay oeiey. – Oe?aeineee
ainoaea?noaaiiue oeieei-oaoiieiae/aneee oieaa?neoao, Aeiai?iiao?iane,
1999.
Aeenna?oaoeey iinayuaia enneaaeiaaieth i?ioeanna eiiieaeniia?aciaaiey
eiiia Ru(IV) n ieneeeneioaie e aai eniieueciaaieth i?e
aieueoaiia?iiao?e/aneii ii?aaeaeaiee ?ooaiey.
Aeey onoaiiaeaiey aiciiaeiuo oi?i nouanoaiaaiey eiiia Ru(IV) a
iaeiiieaene?othueo aiii- e aaoa?iaaiiuo n?aaeao aia?aua i?iaaaeaiu
?an/aou oa?iiaeeiaie/aneie onoie/eainoe ?acee/iuo oeie/aneeo oi?i
?ooaiey. Onoaiiaeaiu i?aaeaeu iaeanoae aeiieie?iaaiey iiiiia?iie e
oao?aia?iie oi?i aeae?ienieiiieaenia Ru(IV), enneaaeiaaiu oneiaey
onoie/eainoe aeae?ieneaeia Ru(IV) e Ru(III) (oaae.1), iino?iaiu
iiaeeoeoee?iaaiiua aeeaa?aiiu O?inoa e Io?aa aeey nenoai Ru-H2O (?en.1)
e Ru-Cl–H2O.
Iaoiaeii eiiiiai iaiaia ii?aaeaeaiu n?aaeiee ca?yae aeae?ienieiiieaenia
Ru(IV) e n?aaeiyy noaiaiue iieeia?ecaoeee, eioi?ua oeacuaatho ia
ninouanoaiaaiea a ii?aaeaeaiiuo oneiaeyo iiiiia?iie e oao?aia?iie oi?i
eiiia Ru(IV). Enneaaeiaaiu aieueoaiia?iua oa?aeoa?enoeee eiiia Ru(IV) a
ia?oei?aoiuo ?anoai?ao. Iieacaii, /oi a caaeneiinoe io ?I ?anoai?ia
ainnoaiiaeaiea eiiia Ru(IV) ec ia?oei?aoiuo ?anoai?ia ia ?.e.y.
neacuaaaony ia aieueoaiia?ia?aiia ?aciui eieee/anoaii e?eauo: +0.075 A,
-0.400 A, -0.550 A (?I=1.50) (ian.e.y.). Ainnoaiiaeaiea iineo
iaia?aoeiue oa?aeoa? e ineiaeiaii aeey ia?aiai e o?aoueaai i?ioeanna
o/anoeai eiiia aiaei?iaea, i?e?iaea oiea – aeeoooceiiiay n eeiaoe/aneeie
ia?aie/aieyie, eioi?ua oneeeaathony n oiaiueoaieai eiioeaio?aoeee eiiia
aiaei?iaea a ?anoai?a. I?aaeeiaeaiu noaiu ainnoaiiaeaiey iiiiia?iie e
oao?aia?iie oi?i aeae?ienieiiieaenia Ru(IV) a Ru(III): Ru3+ e Ru(OH)2+,
a oaeaea Ru(III) a Ru(II) (o?aai. 9-13).
Aia?aua enneaaeiaaii eiiieaeniia?aciaaiea eiiia Ru(IV) a ia?oei?aoiuo
?anoai?ao n eeiiiiie e aeiiie ieneeeneioaie e uaaaeaaie aeeea?aiiiaie
eeneioie. Onoaiiaeaiu noaiu eiiieaeniia?aciaaiey (o?aai.14-16) e
iieacaii, /oi a neaaieeneuo n?aaeao ia?acothony eiiieaeniua eiiu: I –
[Ru(C6H6O7)2(OH)x(H2O)2-x]-x (pH=1.80-2.20), II –
[Ru(C4H5O6)(OH)x(H2O)5-x]3-x (pH=1.40-3.30), III –
[Ru(C2O4)(OH)x(H2O)2-x]-x (pH=1.44-2.44). Niioaaonoaothuea eiiieaeniua
eiiu ainnoaiaaeeaathony ia ?.e.y. i?e Aie=+0.014 A (?), -0.092 A (??), –
0.120 A (???); i?ioeann ainnoaiiaeaiey iineo iaia?aoeiue oa?aeoa? e ia
ineiaeiai o/anoeai eiiia aiaei?iaea.
A uaei/iuo ?anoai?ao (?I>8.0) a i?enoonoaee oeeo?ao- e oa?o?ao-eiiia
Ru(IV) ia?acoao eiiieaeniua niaaeeiaiey, eioi?ua oa?aeoa?ecothony
iaeneioiii iiaeiuaiey liao=540 ii e iioaioeeaeii ainnoaiiaeaiey Aie=
-0.570 A aeey oeeo?aoiiai eiiieaena e liao=715 ii e Aie= -0.300 A aeey
oa?o?aoiiai eiiieaena. Ninoaa eiiieaeniuo niaaeeiaiee ia onoaiiaeai.
A ?anoai?ao n ieceei niaea?aeaieai ?ooaiey iaia?oaeaiu ianeieueei
eaoaeeoe/aneeo aiei (?en.2). Iieacaii, /oi oaeiaiie a aiaeeoe/aneii
aniaeoa yaeyaony aieia n Aie= -0.970 A. Oa?aeoa? yoiai yeaeo?iaeiiai
i?ioeanna, niaeanii eeanneoeeaoeee Ieeieueniia-Oaeia, niioaaonoaoao
eaoaeeoe/aneiio i?ioeanno n iaia?aoeiui ia?aiinii yeaeo?iiia n
iineaaeothuae oeie/aneie ?aaeoeeae. Enneaaeiaaiey i?e?iaeu oiea niaeanii
e?eoa?ey nei?inoe lg Iie/S – lgn, Iie – n1/2 e oaiia?aoo?iie caaeneiinoe
oiea oeacuaatho ia iaee/ea i?aaeuaeouae oeie/aneie ?aaeoeee. A
i?enoonoaee ieneeeneio iaaethaeaaony oeo/oaiea oi?iu aieueoaiia?ia?aiiu,
oaaee/aiea oiea (iaeaieaa cia/eoaeueiia a i?enoonoaee eeiiiiie eeneiou)
e ?anoe?aiea aeeaiaciia ?I enneaaeiaaiee i?ioeanna aei 6.0 (a
ia?oei?aoiuo ?anoai?ao oieueei aei 4.0). I?enoonoaea ieneeeneio e
uaaaeaaie eeneiou ia eciaiyao i?e?iaeu i?ioeanna e i?e?iaeu oiea.
Eaoaeeoe/aneee i?ioeann ineiaeiai o/anoeai eiiia aiaei?iaea a
yeaeo?iaeiie ?aaeoeee, i /ai naeaeaoaeuenoaoao caaeneiinoue iioaioeeaea
Aie io ?I (?en.3). A i?enoonoaee ieneeeneio e uaaaeaaie eeneiou yoa
caaeneiinoue ia ia?ooaaony. Neea oiea n oiaiueoaieai eeneioiinoe
?anoai?ia oiaiueoaaony iinoaiaiii aeey ?anoai?ia n uaaaeaaie eeneioie, a
aeey ia?oei?aoiuo ?anoai?ia (?en.3) e ?anoai?ia n ieneeeneioaie
nouanoaoao ieiuaaeea oiea.
Onoaiiaeaii, /oi a i?enoonoaee oei?eae- e ieo?ao-eiiia a ?anoai?ao
Ru(IV) iaaethaeaaony oaaee/aiea eaoaeeoe/aneiai oiea. Iieacaii, /oi a
i?enoonoaee oei?eaea yoi naycaii n ia?aciaaieai e iineaaeothuei
aeiieie?iaaieai oeie/aneeo oi?i Ru(IV) e Ru(III): Ru(OH)2Cl42-, RuCl52-,
RuCl63-. A neo/aa ieo?aoa oaaee/aiea oiea naycaii n yooaeoii
aieiia-ieeneeoaey. Noaia yeaeo?iaeiiai i?ioeanna i?aaenoaaeaia
o?aaiaieai 17.
Yeaeo?iaeiue i?ioeann n Aie= -0.970 A eniieueciaai aeey ?ac?aaioee
iaoiaeeee aieueoaiia?iiao?e/aneiai ii?aaeaeaiey ?ooaiey. ?ac?aaioaiiay
iaoiaeeea – /oanoaeoaeueia (ieaeiee i?aaeae iaia?oaeaiey 5.00*10-7
iieue/e), naeaeoeaia (enneaaeiaaii aeeyiea 18 eiiia; aeaeaci ia iaoaao
i?e 300-e?aoiii ecauoea), eiaao oe?ieee eioa?aae eeiaeiinoe caaeneiinoe
neea oiea – eiioeaio?aoeey ?ooaiey (1.00*10-6-3.50*10-5 iieue/e).
Iaoiaeeea eniieueciaaia aeey aiaeeca iieoi?iaiaeieeiauo iano,
niaea?aeaueo aeaeaci e ieaoeio, a oaeaea i?e aiaeeca nieaaia nenoai
Nd-Ru-Mn-Si, Ce-Ru-Ga, Ho-Ru-Ga. Iaoiaeeea – yeni?annia e aiaae?aia a
aiaeeoe/aneeo eaai?aoi?eyo AeC EI?OA e IEE “Iiinoa?a”.
Eeth/aaua neiaa: eiiieaeniia?aciaaiea, ieneeeneiou, eaoaeeoe/aneee
yooaeo, aieueoaiia?iiao?e/aneia ii?aaeaeaiea, ianoa, nieaa,
/oanoaeoaeueiinoue, naeaeoeaiinoue.
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